Synthesis and Reactivity of Dinuclear Complexes Containing η<sup>2</sup>-Phenyl−Metal Interactions. Crystal Structures of [NBu<sub>4</sub>][(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>Pt{μ-Ph<sub>2</sub>PCH<sub>2</sub>PPh(η<sup>2</sup>-Ph)}Pt(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>] and [NBu<sub>4</sub>][(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>Pt(μ-dppm)Pt(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>(CO)]
作者:José M. Casas、Juan Forniés、Francisco Martínez、Angel J. Rueda、Milagros Tomás、Alan J. Welch
DOI:10.1021/ic9808753
日期:1999.4.1
Reaction between [NBu4][Pt(C6F5)(3)(dppm-kappa(1)P)] and cis-[M(C6X5)(2)(thf)(2)] (M = Pt, Pd; X = F, Cl; thf = tetrahydrofuran) leads to dinuclear derivatives with dppm Ligands bridging two metal centers: [NBu4][(C6F5)(3)Ptmu-Ph2PCH2PPh(eta(2)-Ph)}M(C6X5)(2)] [X = F, M = Pt (1), M = Pd (2); X = Cl, M = Pt (3), M = Pd (4)]. The structural characterization of complex 1 by single-crystal X-ray diffraction (orthorhombic system, space group Fdd2, with a = 26.520(7) Angstrom, b = 83.69(3) Angstrom, c = 13.835(5) Angstrom, V = 30706(11) Angstrom(3), and Z = 16) reveals two square-planar platinum(II) fragments sharing a dppm ligand with a eta(2)-phenyl-platinum interaction between a phenyl ring of the dppm ligand and one platinum center. This weak eta(2)-phenyl-platinum interaction can be easily displaced by addition of ligands such as CO (giving complex 5), PPh3 (6), or p-toluidine (7). The structure of 5 was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group Pn, with a = 12.259(2) Angstrom, b = 16.375(3) Angstrom, c = 18.851(4) Angstrom, beta = 100.99(3)degrees, V = 3714.8 Angstrom(3), and Z = 2. The complex consists of two square-planar platinum(II) fragments with the dppm ligand acting as a conventional bridge.